WO2019044650A1 - Résine pour moulage de mousse, article moulé en mousse, et procédé de production d'un article moulé en mousse - Google Patents

Résine pour moulage de mousse, article moulé en mousse, et procédé de production d'un article moulé en mousse Download PDF

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Publication number
WO2019044650A1
WO2019044650A1 PCT/JP2018/031131 JP2018031131W WO2019044650A1 WO 2019044650 A1 WO2019044650 A1 WO 2019044650A1 JP 2018031131 W JP2018031131 W JP 2018031131W WO 2019044650 A1 WO2019044650 A1 WO 2019044650A1
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Prior art keywords
foam
resin
molding
molded article
density polyethylene
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PCT/JP2018/031131
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English (en)
Japanese (ja)
Inventor
孝明 染谷
尊 佐野
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キョーラク株式会社
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Application filed by キョーラク株式会社 filed Critical キョーラク株式会社
Priority to CN201880047788.8A priority Critical patent/CN110945062B/zh
Priority to EP18852161.1A priority patent/EP3677401B1/fr
Priority to KR1020207007936A priority patent/KR102557789B1/ko
Priority to US16/640,076 priority patent/US11434342B2/en
Publication of WO2019044650A1 publication Critical patent/WO2019044650A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
    • B29C44/507—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying extruding the compound through an annular die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/34—Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/475—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pistons, accumulators or press rams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B29C49/04116—Extrusion blow-moulding characterised by the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/22—Tubes or pipes, i.e. rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Definitions

  • the present invention relates to a resin for foam molding, a foam molded body, and a method for producing a foam molded body.
  • a tubular air conditioning duct for ventilating air is used.
  • a foam molded body using a foamed resin obtained by foaming a thermoplastic resin with a foaming agent is known.
  • Foam molded articles are in increasing demand because they can simultaneously achieve high thermal insulation and weight reduction.
  • a blow molding method in which a foamed resin in a molten state is clamped with a split mold and air is blown into the interior to expand it.
  • Patent Document 1 discloses a technology for setting the melt tension (MT) to a predetermined value or more and setting MT ⁇ melt flow rate (MFR) to a predetermined value or more in order to increase the expansion ratio of the foam molded product in foam molding. ing.
  • Patent Document 1 Although the criteria disclosed in Patent Document 1 are applicable to various raw material resins, MT and MT ⁇ MFR and the obtained foam are obtained for low density polyethylene (LDPE) used for the raw material resin for foam molding. As a result of examining the relationship of the expansion ratio of the molded product, it was found that the expansion ratio may become low although the values of both MT and MT ⁇ MFR are relatively high.
  • LDPE low density polyethylene
  • This invention is made in view of such a situation, and provides the resin for foam molding containing LDPE which can raise a foaming ratio.
  • a resin for foam molding which is a resin for foam molding containing low density polyethylene, wherein the low density polyethylene has a strain hardening degree of 0.40 or more.
  • the inventors of the present invention conducted intensive studies and found that when the degree of strain hardening of LDPE is 0.40 or more, a foamed molded article having a high expansion ratio can be obtained, and the present invention has been accomplished. .
  • the foam molding resin further contains high density polyethylene.
  • the mass ratio of the low density polyethylene to the high density polyethylene is 2: 8 to 8: 2.
  • the melt tension of the low density polyethylene is 250 mN or more.
  • the shear viscosity of the low density polyethylene is 450 Pa ⁇ s or more.
  • a foam molded article obtained by molding the above-described foam molding resin.
  • a melt-kneaded resin obtained by melt-kneading the above-described foam molding resin and a foaming agent in a foam extruder is extruded from the foam extruder to form a foam parison, and the foam parison is obtained.
  • a method for producing a foam molded article comprising the steps of molding to obtain a foam molded article.
  • FIG. 6 is a graph plotting the relationship between strain hardening degree and expansion ratio in Examples 1 and 2 and Comparative Examples 1 to 5.
  • FIG. 7 is a graph plotting the relationship between MFR ⁇ MT and expansion ratio in Examples 1 and 2 and Comparative Examples 1 to 5.
  • Foam molding resin The foam molding resin according to the embodiment of the present invention is a foam molding resin containing LDPE, and the LDPE has a strain hardening degree of 0.40 or more.
  • ⁇ n ⁇ E (t, ⁇ non-liner ) / ⁇ E (t, ⁇ liner ) (1)
  • ⁇ E (t, ⁇ non-liner ) is a measured value of extensional viscosity during strain hardening
  • ⁇ E (t, ⁇ liner ) is a measured value of extensional viscosity without strain hardening.
  • the uniaxial elongation viscosity ⁇ E (t, ⁇ non-liner ) is a value obtained by measuring at a strain rate of 1 s ⁇ 1 and a measuring temperature of 180 ° C. using ARES-G2 (manufactured by TA INSTRUMENTS)
  • Uniaxial extensional viscosity ⁇ E (t, ⁇ liner ) means the value obtained by measuring at a strain rate of 0.1 s -1 and a measuring temperature of 180 ° C. using ARES-G2 (manufactured by TA INSTRUMENTS) as well.
  • the foam-like resin of this embodiment suppresses the above-mentioned phenomenon by containing LDPE having a high degree of strain hardening, and as a result, it is possible to obtain a foam having a high expansion ratio.
  • the strain hardening degree of LDPE is 0.40 or more, more preferably 0.44 or more, and usually 1.0 or less, for example, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, and O.S. 56, 0.57, 0.58, 0.59, 0.60, 0.70, 0.80, 0.90, 1.00, etc., and any value among these numerical values. It is also good.
  • the melt tension (MT) of LDPE is not particularly limited.
  • the resin for foam molding of the present embodiment when the MT of LDPE is, for example, 250 mN or more, 300 mN or more, LDPE having high resin strength which is predicted to be difficult to increase the expansion ratio in the prior art Among them, it is possible to select and use an LDPE suitable for producing a molded product having a high expansion ratio.
  • melt tension is measured from an orifice of 2.095 mm in diameter and 8 mm in length at a test temperature of 190 ° C. and an extrusion speed of 10 mm / min using a melt tension tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) And the tension when winding this strand on a roller with a diameter of 80 mm at a winding speed of 16 rpm.
  • the shear viscosity of LDPE is not particularly limited, and is, for example, 200 Pa ⁇ s, 250 Pa ⁇ s, 300 Pa ⁇ s, 350 Pa ⁇ s, 400 Pa ⁇ s, 450 Pa ⁇ s, 500 Pa ⁇ s, or the like. It may be a value between any of the above.
  • LDPE having a shear viscosity of, for example, 300 Pa ⁇ s or less, 350 Pa ⁇ s or less, etc. has a resin pressure in the foam extruder too low, so the foam molding resin and foam agent are kneaded in the foam extruder. It was predicted that the resin pressure was too low, the gas for foaming was not sufficiently dissolved in the resin for foam molding, and the foaming ratio was lowered. Further, LDPE having a shear viscosity of, for example, 400 Pa ⁇ s or more, 450 Pa ⁇ s or more, or the like has a small difference between the resin pressure and the gas injection pressure in the foam extruder for kneading the foam molding resin and the foaming agent. It was predicted that the resin would not be compatible with the gas, the gas dispersibility would be low, and the expansion ratio would be low.
  • the resin for foam molding of the present embodiment when the strain hardening degree of LDPE is 0.40 or more, it is predicted that it is difficult to increase the expansion ratio in the prior art also from among LDPE. It becomes possible to select and use a LDPE suitable for producing a molded product having a high expansion ratio.
  • the shear viscosity means a value obtained by measurement at a test temperature of 190 ° C. and an apparent shear rate of 600 / sec according to JIS K-7199.
  • the melt flow rate (MFR) of LDPE in the present embodiment is not particularly limited, but is, for example, preferably 0.2 to 2.5 g / 10 min, more preferably 0.3 to 2.0 g / 10 min, 0.5 It is more preferable that the amount is -1.6 g / 10 min. In this case, the expansion ratio tends to be particularly high.
  • melt flow rate means a value obtained by measurement at a test temperature of 190 ° C. and a test load of 2.16 kg according to JIS K-7210.
  • the foam molding resin of the present embodiment may be made of only LDPE, or may contain another resin.
  • resins other than LDPE include high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • the weight ratio of LDPE to HDPE is not particularly limited, but is preferably 2: 8 to 8: 2, and more preferably 3: 7 to 7: 3. If the proportion of HDPE is too small, the rigidity of the foamed molded article tends to be low, and if the proportion of HDPE is too large, the expansion ratio tends to be low.
  • LDPE and HDPE are mixed in the above ratio, it is possible to obtain a foam molded article having high rigidity and expansion ratio.
  • the physical properties of HDPE are not particularly limited, but preferable MFR, shear viscosity, density and MT are as follows.
  • MFR 0.2 to 0.4 g / 10 min
  • Shear viscosity 550 to 650 Pa ⁇ s
  • Density 0.94 to 0.96 g / cm 3 MT: 70-200 mN
  • the length in the thickness direction of the cells formed in the foam is preferably 50 to 100 ⁇ m. In the case of 50 ⁇ m, the expansion ratio of the foam tends to be small because the growth of the cells is insufficient, and in the case of more than 100 ⁇ m, the foam is likely to be generated to cause pinholes.
  • a melt-kneaded resin obtained by melt-kneading the above-described foam molding resin and a foaming agent in a foam extruder is extruded from the foam extruder. Forming a foam parison, and molding the foam parison to obtain a foam molded body.
  • the obtained foam molded article can be used, for example, in a vehicle air conditioning duct or the like.
  • the foam extruder 1 includes a cylinder 3, a resin inlet 5, a screw 7, a foaming agent inlet P, a temperature control unit 9, a resin extrusion 11, and a die head 12.
  • the resin inlet 5 is a so-called hopper, from which a raw resin is charged.
  • the form of the raw material resin is not particularly limited, but is usually in the form of pellets.
  • the raw material resin is the foam molding resin of the embodiment of the present invention described above.
  • the raw material resin is introduced into the cylinder 3 from the resin inlet 5 and then heated in the cylinder 3 to be melted and become a molten resin. Further, the screw 7 disposed in the cylinder 3 is conveyed toward the resin extrusion port 11 provided at one end of the cylinder 3 by the rotation of the screw 7.
  • the screw 7 is disposed in the cylinder 3 and is conveyed toward the resin extrusion port 11 while kneading the molten resin by its rotation.
  • a gear device 15 is provided at one end of the screw 7, and the screw 7 is rotationally driven by the gear device 15.
  • the number of screws 7 disposed in the cylinder 3 may be one or two or more.
  • the cylinder 3 is provided with a foaming agent inlet P for injecting the foaming agent into the cylinder 3.
  • the position at which the foaming agent injection port P is provided is not particularly limited, but when the position of the end of the cylinder 3 on the resin inlet 5 side is 0 and the position of the end on the resin extrusion port 11 is L, the foaming agent injection port P is preferably provided at a position of 0.3 L to 0.7 L (preferably 0.4 to 0.6 L).
  • the foaming agent injection port P is provided on the resin inlet 5 side more than 0.3 L, the foaming agent may be injected in a state where kneading of the molten resin is insufficient, and the dispersion of the foaming agent may be insufficient. is there.
  • the temperature of the molten resin is usually controlled so as to gradually decrease toward the resin extrusion port 11, the foaming agent is injected when provided on the resin extrusion port 11 side with respect to the foaming agent injection port P0.7L. The temperature of the molten resin at the site may be too low to reduce the amount of blowing agent injected.
  • the blowing agent injected from the blowing agent inlet P includes physical blowing agents, chemical blowing agents, and mixtures thereof, with physical blowing agents being preferred.
  • physical blowing agents inorganic physical blowing agents such as air, carbon dioxide gas, nitrogen gas, water and the like, organic physical blowing agents such as butane, pentane, hexane, dichloromethane, dichloroethane and the like, and their supercritical fluids are used. be able to.
  • a supercritical fluid it is preferable to use carbon dioxide, nitrogen, etc., and if it is nitrogen, its critical temperature is -149.1 ° C, its critical pressure is 3.4 MPa or more, and if it is carbon dioxide, its critical temperature is 31 ° C, its critical pressure It is obtained by setting it as 7.4 MPa or more.
  • a chemical foaming agent what generates carbon dioxide gas by the chemical reaction of an acid (example: citric acid or its salt) and a base (example: sodium bicarbonate) is mentioned.
  • the chemical blowing agent may be injected from the resin inlet 5 instead of injecting from the blowing agent inlet P.
  • the temperature control unit 9 is configured to individually control a plurality of temperature control units provided along the cylinder 3 to control the temperature of each portion of the cylinder 3.
  • the temperature control unit 9 can also control the temperature of the die head 12 for forming a parison and the temperature of the connecting portion 10 between the cylinder 3 and the die head 12.
  • the die head 12 includes a cylindrical die outer cylinder 41 and a mandrel 43 accommodated therein, and stores the melt-kneaded resin extruded from the cylinder 3 in a space 47 therebetween.
  • the ring-shaped piston 45 is pushed down in the vertical direction to push the melt-kneaded resin from the die slit 49 to form the cylindrical foamed parison 13.
  • the die head 12 for forming the cylindrical foam parison 13 is shown, the die head 12 may be for forming a sheet-like foam parison.
  • the foam parison 13 is guided between the pair of split molds 14.
  • a molded foam is obtained by molding the foamed parison 13 using the split mold 14.
  • the molding method using the split mold 14 is not particularly limited, and may be blow molding in which air is blown into the cavity of the split mold 14 for molding, and the inner surface of the split mold 14 from the inner surface of the cavity may be formed.
  • the vacuum parison 13 may be formed by vacuuming it under reduced pressure, or by a combination thereof.
  • the blow molding was performed using the foam parison formed under the above conditions, to produce a cylindrical foam molded article having a diameter of 50 mm, a height of 100 mm, and a thickness of 5 mm.
  • the moldable expansion ratio is simply referred to as the expansion ratio.
  • Table 1 the values of MFR, MT, MFR ⁇ MT, strain hardening degree, and shear viscosity are shown together. MT, MFR, strain hardening degree, and shear viscosity were measured by the method described in the embodiment.
  • FIG. 5 A graph plotting the relationship between strain hardening degree and foaming ratio in Examples 1 and 2 and Comparative Examples 1 to 5 is shown in FIG. 5, and a graph plotting MFR ⁇ MT and foaming ratio is shown in FIG.
  • Examples 1 and 2 and Comparative Examples 1 to 5 are compared, Examples 1 and 2 using LDPE having a strain hardening degree of 0.40 or more show an excellent expansion ratio of 2.5 times or more. You can see that Moreover, when Example 2 and Comparative Example 1 are compared, although the value of MFR ⁇ MT is almost the same value, the value of the foaming ratio is much better in Example 2.
  • Example 2 In Experimental Example 2, using LDPE (grade: 1005FY20, manufactured by Reliance) of Example 2, the mass ratio of LDPE to HDPE was changed to 7: 3, and the mass ratio of LDPE to HDPE was 3: 7. A modified Example 4 was made and the moldable expansion ratio was measured. As a result, the moldable expansion ratio was 3.5 times in Example 3 and 2.4 times in Example 4. The result is that, even when the mass ratio of LDPE to HDPE is 1: 1, the expansion ratio of the foamed molded article can be increased by using LDPE having a strain hardening degree of 0.40 or more. It shows.

Abstract

La présente invention concerne une résine pour moulage de mousse contenant du polyéthylène basse densité, le polyéthylène basse densité ayant un taux d'écrouissage de 0,40 ou plus.
PCT/JP2018/031131 2017-08-30 2018-08-23 Résine pour moulage de mousse, article moulé en mousse, et procédé de production d'un article moulé en mousse WO2019044650A1 (fr)

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CN201880047788.8A CN110945062B (zh) 2017-08-30 2018-08-23 发泡成型用树脂、发泡成型体、发泡成型体的制造方法
EP18852161.1A EP3677401B1 (fr) 2017-08-30 2018-08-23 Résine pour moulage de mousse, article moulé en mousse, et procédé de production d'un article moulé en mousse
KR1020207007936A KR102557789B1 (ko) 2017-08-30 2018-08-23 발포 성형용 수지, 발포 성형체, 발포 성형체의 제조 방법
US16/640,076 US11434342B2 (en) 2017-08-30 2018-08-23 Resin for foam molding, foam molded article, and method for producing foam molded article

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024004940A1 (fr) * 2022-06-30 2024-01-04 キョーラク株式会社 Procédé de fabrication de corps moulé en résine et procédé de fabrication de corps moulé en mousse

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7115371B2 (ja) 2019-03-11 2022-08-09 株式会社デンソー 超音波センサ
JP2023010408A (ja) * 2021-07-09 2023-01-20 住友化学株式会社 エチレン系改質材、エチレン系樹脂組成物、フィルム、エチレン系樹脂組成物の製造方法、および、フィルムの製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001545A (ja) * 2009-05-18 2011-01-06 Mitsui Chemicals Inc 発泡成形用エチレン系重合体、発泡成形用樹脂組成物およびそれらから得られる発泡体
JP2012067256A (ja) 2010-09-27 2012-04-05 Kyoraku Co Ltd 発泡成形体の製造方法
JP2012211312A (ja) * 2011-03-23 2012-11-01 Asahi Kasei Chemicals Corp 自動車内装材成形用基材、それよりなる自動車内装材成形用積層基材
WO2013114996A1 (fr) * 2012-01-30 2013-08-08 キョーラク株式会社 Procédé pour la fabrication d'article moulé en mousse et article moulé en mousse
JP2014058624A (ja) * 2012-09-18 2014-04-03 Tosoh Corp ポリエチレン系発泡中空成形体
JP2014517135A (ja) * 2011-06-23 2014-07-17 ダウ グローバル テクノロジーズ エルエルシー 低散逸率を有する低密度ポリエチレンおよびそれを製造するための方法
JP2015172210A (ja) * 2015-07-08 2015-10-01 日本ポリエチレン株式会社 ポリエチレン系樹脂組成物およびその成形体
JP2015196711A (ja) * 2014-03-31 2015-11-09 サンアロマー株式会社 ポリプロピレン樹脂組成物及びその成形品
JP2015227459A (ja) * 2015-07-07 2015-12-17 日本ポリエチレン株式会社 容器用ポリエチレン樹脂組成物及びそれよりなる成形体
JP2017039812A (ja) * 2015-08-18 2017-02-23 キョーラク株式会社 発泡成形用樹脂、発泡成形体の製造方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002146075A (ja) * 2000-09-04 2002-05-22 Tosoh Corp ポリオレフィン系樹脂発泡体およびポリオレフィン系樹脂組成物
US6414047B1 (en) * 2000-09-04 2002-07-02 Tosoh Corporation Polyolefin foam and polyolefin resin composition
JP2002327011A (ja) * 2001-01-24 2002-11-15 Sumitomo Chem Co Ltd 押出ラミネート加工用エチレン重合体樹脂
DE602006006061D1 (de) 2006-08-25 2009-05-14 Borealis Tech Oy Polypropylenschaumstoff
JP5309903B2 (ja) * 2007-11-08 2013-10-09 住友化学株式会社 押出発泡成形用樹脂組成物および押出発泡成形体
JP2010038565A (ja) * 2008-07-31 2010-02-18 Sumitomo Chemical Co Ltd 熱可塑性樹脂の評価装置及びその利用
JP5360975B2 (ja) * 2009-05-01 2013-12-04 株式会社ジェイエスピー ポリエチレン系樹脂発泡ブロー成形体の製造方法およびポリエチレン系樹脂発泡ブロー成形体
JP2013124300A (ja) * 2011-12-14 2013-06-24 Asahi Kasei Chemicals Corp 無架橋発泡用ポリエチレン系樹脂組成物
JP2014046549A (ja) * 2012-08-31 2014-03-17 Tosoh Corp 金属部材−ポリエチレン発泡部材複合体及びその製造方法
US10822479B2 (en) 2012-09-20 2020-11-03 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
JP6468413B2 (ja) * 2013-10-10 2019-02-13 キョーラク株式会社 発泡ブロー成形品及び発泡ブロー成形方法
WO2016141179A1 (fr) * 2015-03-04 2016-09-09 Berry Plastics Corporation Matière polymère pour contenant

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001545A (ja) * 2009-05-18 2011-01-06 Mitsui Chemicals Inc 発泡成形用エチレン系重合体、発泡成形用樹脂組成物およびそれらから得られる発泡体
JP2012067256A (ja) 2010-09-27 2012-04-05 Kyoraku Co Ltd 発泡成形体の製造方法
JP2012211312A (ja) * 2011-03-23 2012-11-01 Asahi Kasei Chemicals Corp 自動車内装材成形用基材、それよりなる自動車内装材成形用積層基材
JP2014517135A (ja) * 2011-06-23 2014-07-17 ダウ グローバル テクノロジーズ エルエルシー 低散逸率を有する低密度ポリエチレンおよびそれを製造するための方法
WO2013114996A1 (fr) * 2012-01-30 2013-08-08 キョーラク株式会社 Procédé pour la fabrication d'article moulé en mousse et article moulé en mousse
JP2014058624A (ja) * 2012-09-18 2014-04-03 Tosoh Corp ポリエチレン系発泡中空成形体
JP2015196711A (ja) * 2014-03-31 2015-11-09 サンアロマー株式会社 ポリプロピレン樹脂組成物及びその成形品
JP2015227459A (ja) * 2015-07-07 2015-12-17 日本ポリエチレン株式会社 容器用ポリエチレン樹脂組成物及びそれよりなる成形体
JP2015172210A (ja) * 2015-07-08 2015-10-01 日本ポリエチレン株式会社 ポリエチレン系樹脂組成物およびその成形体
JP2017039812A (ja) * 2015-08-18 2017-02-23 キョーラク株式会社 発泡成形用樹脂、発泡成形体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3677401A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024004940A1 (fr) * 2022-06-30 2024-01-04 キョーラク株式会社 Procédé de fabrication de corps moulé en résine et procédé de fabrication de corps moulé en mousse

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KR20200046055A (ko) 2020-05-06
US20210130563A1 (en) 2021-05-06
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CN110945062B (zh) 2022-06-24
EP3677401A4 (fr) 2020-10-07
EP3677401B1 (fr) 2022-10-05
JP6963171B2 (ja) 2021-11-05
KR102557789B1 (ko) 2023-07-19
CN110945062A (zh) 2020-03-31
EP3677401A1 (fr) 2020-07-08

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